Production of 1, 4-dihydroxy-alkylaminoanthraquinone



UNITED ST Patented Sept. 7,

The present producing ones.

invention We have found that1,4-dihydroxyalkylaminoth manner anthraquinqnes are obtained in a smoo rRonUc'rIoN F AMINOAN Karl Koeberl'e' and Christian Steigerwald, Ludwigshafen on-the to General Aniline N. Y., a corporation of Delaware -'-Ithine, Germany,

assignors Works, Inc., New York,

No Drawing. Application April 18, 1936, Serial No. 75,230. In Germany April 20, 1935 2 Claims. (01. 260-450) relates to a" 'proces 1,4 dihydroxyalkylaminoanthraquins PATENT IA-DIHYDROXY-ALKYh. THRAQUINONE fin waxes, benzine, petroleum and otherhydro- I carbons, lacquers or artificialcompositions. i

The following examples will further illustrate how the said invention is carried out in practice 5 but the invention is not restricted to these exby heating an anthraquinone containing in the 1- amples. The parts are by Weight. position a group --NHR. in which R is a member x b selected from the class consisting of hydrogen. l v and the alkyl, aralkyl, cycloalkyl, aryl and acyl A mixture of 20 parts, f 1,4-diaminoanthragroups, and in the 4-position' a substituent sequinone and 100 parts of ethanolamine is heated lected from the class consisting of the hydroxyl, for about an hourat about 150 C. whil'e'stirring. nitro, amino, alkylamino, aralkylamin cyclo- The mixture is allowed to 'cool, diluted"with alkylamino and arylamino groups, with at least methanol and the resulting compound filtered off two molecular proportions of ahydroxyalkylamby suction, washedwith methanoland dried.

.5 ine, until 'the groups in the land 4-positions The known compound IA-dihydrOXyethylamino- 5 are replaced by the radical of the hydroxyalkylanthraquinone is thus obtained in the form of amine. 4 blue crystals. It dyes acetateartificial silk blue As initial materialswhichare especiallysuitshades. l y l T able for the process accordingto thisinvention The same compound is obtained by employing maybe mentioned 1,4-diarnino-anthraquinone, 1-amino-4-nitroanthraquinone; l-methylamiiiog0 1,4,5-triaminoanthraquinone, l,4,5,8-tetramino- 4-aminoanthraquinone, 1,4 dimethylaminoan anthraquinone, 1 amino-4-hydroxyanthraquinthraquinon'e or 1-methylamino l hydroxyethyl one,l arnino alkylamino nthraquinones,l-arnaminoanthraquinone instead of l'A-di'aminoanino-e-nitroanthraquin'ones, 1,4-dialkylamin0anthraquinone. The corresponding lA-dihydroxythraquinones, 1;5-diamino-4,s-dihydroxyanthrapromdaminoanthraquinone is obtained by'em} quinone, 1,8diamino-4=,5dihydroxyanthraquinp e 1,2-pr0r1an01amine r -pr pano am 'neone, 1-amino-4-acylaminoanthraquinones, l-aminstead of ethanolamine inc-4-arylaminoanthraquinones, 1-amino-4-hexmb ahydroarylaminoanthraquinones, l-arnino--aralkylaminoanthraquinones, lA-diarylaminoan- A mixture of 20 parts o Y f Y- 30 thraquinones, 1A-dihexahydroarylaminoanthra a t r q and 30 Parts Of fl-p l fi mquinones, 1,4-diaralkylaminoanthraquinones, 1- ine is heated while stirring at from 125 .to' 1'30 aralkylamino-4-hexahydroarylaminoanthraquin- C. until the solution has become pure blue. The ones, 1-alkylamino-4arylaminoanthraquin ne mixture is then allowed to cool, diluted with l-alkylaminoA-hexahydroarylaminoanthraquinmethanol e resulting Y yp py1'- ones and l-allzylamino-4aralkylaminoanthraamino (1,2) anthraquinone is filtered-off by sub quinones. tion, washed with methanol and dried. It yields AS y xyalkylamines which are espec y blue dyeings on acetate artificial silk. suitable for the reaction may be mentioned eth- In 9, imi1ar manfier 1 5;diamin' -4 8 dihy;.

40 anqlamine, the propanolamines and the blita'noldroxyanthraquinonemay be caused to react with ammespropanolamine, a blue'dy estiifi is then likewise The rewiion is g ne l Speakmg earned out obtained which yields very powerful dyeings on while heating, for example at temperatures be- 'cetate artificial Silk. M tween about 100 and about 150 C. In many i 5 cases the reaction may advantageously be carried Example 3 out f Superatmospheric pressure n A mixture of 20 parts of 1,4,5,8-tetraminomore 1S freqpenuy preferable wolrk anthraquinone and 100 parts of ethanolamine is Presence of dnuent Such as me ano 6 mm heated for about three hours while stirring at isobutanol or monochlorbenzene. 150 C Th t n w d to O 1 and The compounds obtainable according to this 8 mm me Is 0 e c O 50 invention are usually obtained in very good yields muted Wlth methanol- T e resulting dark blue and in a State of high purity They may in most crystals are filtered off by suction and dried. cases be employed with advantage for dyeing cel- They yield on a t ar fi a k p w fu lulose esters and ethers. They may also be emblue dyein s the Shades Of which are displaced ployed in part for dyeing fats, oils, waxes, paraftowards green as compared with those of the 55 dyeings obtained with the initial material artificial light.

and

heated at 150 C. While stirring until the solution has become blue. It 18 then allowed to cool instead of The compound yields powerful blue dyeings on acetate artificial silk.

Similar blue dyestuffs are obtained by employing for example 1-amino-4-hydroxyanthraquinone, l-amin4-nitroanthraquinone, l-methylamino4aminoanthraquinone, 1,4,5,8-tetraminodiaminoanthraquinon'e.

Example 5 A mixture of 20 parts of lA-di-normal-butylaminoanthraquinone and 100 parts of ethanolamine is heated at 150 C. for about half an hour 1,4 dihydroxyethylaminoanthraquinone thus obtained dyes shades.

The same compound is obtained by employing instead lA-di-normal-butylaminoanthramal-amylaminoanthraquinone, 1 -ethylamino-4- normal-propylaminoanthraquinone, l-normalbutylamino 4 hydroxypropylaminoanthraquinone Example 6 A mixture of 10 parts of 1,4-dianilidoanthraquinone and 50 aminoanthraquinone thus obtained in the form of blue crystals shades.

The same compound is obtained by employing, instead of 1,4-dianilidoanthraquinone, lmethylamino-4-anilidoanthraquinone, l-methylamino 4 toluidoanthraquinone, 1 methylamino-4-benzylaminoanthraquinone, l-anilido- 4-cyclohexylaminoanthraquinone or l-benzylamino-4cyclohexylaminoanthraquinone.

Example 7 case 1.4-dihydroxyethylaminoanthraquinone is obtained as the reaction product.

and

It is a blue powder which dyes acetate artificial silk blue shades.

Instead of the said initial compound, the compounds serving as starting materials in EX- amples 6 and 7 may be employed.

What we claim is:

1. A process of producing 1,4-dihydroxyalkylaminoanthraquinones Which comprises heating and the alkyl, aralkyl, cycloalkyl,

amine, until the groups in the 1- and 4-positions are replaced by the radical of the hydroxyalkylamine.

2. A process of producing 1,4-dihydroxyethylaminoanthraquinone which comprises heating KARL KOEBERLE. CHRISTIAN STEIGERWALD. 

